Alkylolamine derivatives of aliphatic acids



Patented Feb. 6, 19

Pont de Nemours &

DEBIVAS F ill" ACIDS Jean Georges Ke'm, Waltham, Mesa, and Charles J. Sala, Wilmington, DeL, assignors to E I. du

Company, Wilmington,

DeL, a corporation of Delaware No Drawing. Original application August .4, 1927,

Serial No. 210,714. Divided and this application March 21, 1930. Serial No. 437,937

20 Claims. (01. 260-112) This case is a division of our copending aplication Serial No. 210,714, filed August 4, 1927 now Patent No. 1,799,821, dated April '7, 19'31.

This invention relates to alkylolamine salts of 5 aliphatic acids both saturated and unsaturated and to the sulfonic acid derivatives of these acids and more particularly to the ethanolamine salts of the higher fatty acids.

This invention has as objects the preparation of soluble oils, solvents and detergents as well as 'of antiseptic soaps. 5

These objects are accomplished by making the salts of the bases known as alkylolamines or hydroxy-alkylamines, more particularly of the ethanolamines, by combination with the fatty acids mentioned above by any of the well known methods for the production of salts.

The bases used for our purpose may be repre sented by the following general'formula:

Alk-OH NQRI where Alk represents an aliphatic or hydroxy aliphatic radical, R1 and R2 represent hydrogen or an aliphatic radical or a hydroxy aliphatic radical or a poly hydroxy aliphatic radical. In making these new soluble oils we may proceed as follows:

The free fatty acids are combined with an organic base or a mixture of such bases. If the fatty acid is a solid the preparation is aided by the application of heat. It is also possible to start from the glycerides of the fatty acids, 1. e., olive oil, cottonseed oil, castor oil, linseed oil and the like by saponifying the glycerides by heating with the base to a high temperature. In this case we find that the reaction is complete when a sample of the mixture dissolves entirely'in wa- 40 ter. Ii water is present at the start this may be driven off, the base not being volatile, until a concentrated product is left behind. when u. .1. .1 these products by this method it is found that an excess of base is necessary to give the most 4 satisfactory results.

when preparing the products obtained from the 0 fonated imsaturated acid as obtained by action of sulfuric acid on an unsaturated oil such as castor oil in the wellknown manner isfreed of mineral acid by washing. It is then freed of water either by settling or by any other suitable means and then enough of the alkylolamine base is added at ordinary temperature to neutralize the acidity of the sulfonic'acid group or of both sulfonic acid andthe 'carboxylic acid groups. The following exampleswill serve to illustrate our method of procedure but itis to be understood that the invention is not to be limited there- Example 1 2823.7 parts of free oleic acid are mixed with 1490 parts of tri-ethanolamine.

Example 2 1960 parts of oleic acid are mixed with 950 parts of a mixture containing triethanolamineand 20% of di-ethanolamine.

The products resulting from this procedure are I semi-solids, particularly water soluble and ready for use without further treatment. It is possible that the resultant material may be a compound of the base with the. oleic acid but this has not been definitely established and is, in fact, im-

material to the success of the invention.

' Example 3 372 parts castor oil are mixed wit 260 parts tri-ethanolamine 200 parts water. The above mixture is heated on the water bath for several hours; The saponification proceeds slowly and in order to make it complete within reable time it is of advantage to add an excess, for example 30% tri-ethanolamine, above the quantity mentioned.

' Example 5 of stearic acid are melted. late the stirred J w tri-ethanolamine -stirring is con;

282 parts oleic acid 91 parts or amino-propane diol NHs-OHf-OH-OHr-OH are heated together until completely mixed. The

product is very soluble in alcohol. In water the solution is cloudy but becomes clear on the addition of some excess base, e. g. 15 to 20%.

Example 7 282 parts oleic acid are caused to react as given in the above example with 119 parts of methyl di-ethanolamine The soap obtained in this way has the property, when in alcoholic solution, of dissolving mercuric oxide and giving a relatively stable product soluhis in water. This is altogether a surprising result and illustrates the use of these new soaps for pharmaceutical purposes.

Example 8 6 parts of a crude sultonated oil made. by the action oi? sulfuric acid on castoroil are mixed with r 1 part 01 mono-ethanolamine Example 9 2.7 parts of a crude sulionated oil mixture in f the 10m 01 free acids are mixed with 1 part or a mixture of diand tri-ethanolamine. The products of Examples 8 and 9 are entirehr soluble in water. They are thick yellow oils presumably containing salts of the bases of the sulionic acids but this point has not been definitely established and is immaterial to the success of the invention. The products formed in this way are quite satisfactory for ordinary purposes.

In dyeing Ponsol Blue on double paste, Schultz No. 842, on cotton yarn in the package machine, using- 5% of color %7 sodium hydroxide 3% hydrosulfite, the addition of 1% of theproductformed by combining 1 mole or 'sulio-ricinoleic acidand 1 mole tri-ethanolamine, containing di-ethanolamine, results in a brighter, more level dyeing.

Example 10 If a pure product is needed the operation may be carried out as follows:

378 parts or pure sulto-ricinoleic acid prepared iby theaction of chloro-suli'onic acid on pure ricinoleic acid are mixed with 149 parts of tri-ethanolamine. In the above case the addition of a further molecular equivalent'oi' base produces a more soluble oil. The reason may be that the extra quantity of base combines with the carboxyl group but again this point has not been determined.

In the above examples any one .of the bases as defined by the general formula-given above may be used either aloneor in mixture. The

fatty acids may also be varied through a wide range.

We have found that these products, which are. essentially organic soaps possess a greater dissolving power or dispersing power for organic substances than do ordinary soaps. They possess the detergent property of soaps without the high alkalinity characteristic of sodium or potassium salts of the fatty acids. These products for-these reasons have a distinct advantage for many purposes and particularly .as assistants in dyeing, and those compounds which are derived from 95 sulfonated castor oil by the process mentioned are in many ways superior to ordinary sulfonated oils. Their superiority is evidenced by the greater evenness of the shades developed, the better utilization of the color, and the greater brilliance of the dyeing.

When added to water they bring about solution or dispersion. in so fine a form as to appear a solution of insoluble organic bases such as amino-azo-benzene, para-nitro-befiaene, azo -diphenylamine, benzene azo naphthalene azophenol, Rosanthrene base, di-ethyl-para-amidophenol-1:4 naphtho-quinone-mono-imide, 2.4 dinitro-benzene-l-azo-di ethyl-aniiine, etc. It takes about 2 to 5 parts of the solvent for 1 part o! the insoluble base. These solutions may be used very successfully for the purpose of dyeing fibers of esterified cellulose. 3 I

It has also been found that these s'oapsdissolve metallic hydroxides and oxides, for example, mer- 5 curic oxide, and this property indicates their probable value in pharmacology, for example, in the production of antiseptic soaps and the like.

As many apparently widely diflerent embodiments oi. this-invention'may be made without 20 departing from the spirit thereof, it is to be understood that we do not intend to limit ourselves. to the specific embodiments thereof except.as.indi-. cated in theappended claims.

We claim; 5

1. A product resulting from the chemical combination of an acid taken from the group consistj ing of oleic, stearic and ricinoleic acids with an alkylolamine containing a plurality of alkyl groups.

2. A product resulting from the chemical combination of an acid taken from the group consisting of oleic, stearic and ricinoleic acids with an ethanolamine containing a plurality of ethyl groups.

3. A product resulting from the-chemical combination of an acid taken from the group consist ing of oleic, stearic and ricinoleic acids with at least one or the substances consisting of diethanolamine and. tri-ethanolamine.v 14

4. A product resulting from the chemical combination of an'acid taken from the group consisting of oleic, stearic and ricinoleic acids with an amine from the group consisting of di-ethanolamine, tri-ethanolamine, and amino-propane diol.

5, A product resulting from the chemical combinatibn 0! an acid taken from the group consisting of oleic, stearic and ricinoleic acids with triethanolamine. 150

6. A product resulting from the chemical-combination of stearic acid with an alkylolamine containing a plurality of alkyl groups.

7. A product resulting from the chemical combination of stearic acid with an ethanolamine containing a plurality of ethyl groups.

8. A product resulting from the chemical combination of stearic acid with di-ethanolamine.

13. A product resulting from the chemical combination of stearic acid with amino-propane diol.

14. As new compounds, the reaction products of alkyl-hydroxyl amines with ricinoleic acid.

15. As new compounds, the reaction products of ethanolamines with ricinoleic acid.

16. As a new compound, trlethanolamine ricinoleate.

1'1. A productv resulting -from the chemical combination of a higher fatty acid with an alkylolamine containing a plurality of alkyl groups.- I

18. A product resulting from the chemical combination of a higher fatty acid-with an ethanol- .amine containing a plurality of ethyl groups.

19. A product resulting from the chemical combination of a higher fatty acid with at least one of -the substances consisting of diethanolamine and triethanolamine. I

20. A product resulting from the chemical combination of a higher fatty acid with an amine fromthe group consisting of diethanolamine,

triethanolamine, and amino propane diol.

JEAN cnoaans KERN. cnamns J. SALA. 

